DE1125659B - Process for the production of a glycidyl polyether from a polyhydric phenol - Google Patents

Description

GERMAN

PATENT OFFICE

INTERNAT. KL.

PaI Bl. V,

iieues.
ti

■ <*

REGISTRATION DAY:

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL:

NOVEMBER 28, 1957

MARCH 15, 1962

Glycidyl polyethers of polyhydric phenols are previously by etherifying a polyhydric phenol with Epichlorohydrin in an alkaline medium, e.g. B. using sodium hydroxide been. However, the liquid polyethers obtained by this method are quite high Viscosities, and when used for certain purposes, such as adhesives, for the manufacture of Layered bodies or surface coatings, an addition of liquid diluents was previously necessary. Even the addition of such diluents was in many cases unsatisfactory, since their presence has an adverse effect on the properties of the cured products can.

It has now been found that these disadvantages are avoided and relatively low molecular weight glycidyl polyethers can be obtained, which are very suitable as solvent-free paints.

According to the invention, a polyhydric phenol with more than an equivalent amount of an epihalohydrin is used and with an alkali hydroxide in the presence of 0.1 to 13 percent by weight of one implemented monohydric phenol. If these special measures are used, then there is a single value Phenol in certain amounts during the formation of the epoxy resins in the reaction mixture, and liquid compositions are obtained which contain the glycidyl polyethers of polyhydric phenols and have surprisingly low viscosities.

For example, a liquid glycidyl polyether made from 2,2-bis- (4-oxyphenyl) propane in the usual way is produced, a viscosity of about 140 to 160 poise at 25 ° C, while that according to the invention glycidyl polyether made from the same polyhydric phenol has a very low viscosity of have only 27.

Furthermore, the products according to the invention with low viscosity can under Formation of insoluble, infusible products, which are hardened from the products with high viscosity produced are at least equivalent and in many cases even superior. This finding was surprising in view of the fact that previous attempts to down- +5 Setting the viscosity of glycidyl polyethers always only leads to the formation of hardened products with bad ones Properties have led.

The monohydric phenols to be used in the process according to the invention have a only OH group bonded directly to the aromatic ring. The connections can be one or Method of manufacture

of a glycidyl polyether

from a polyhydric phenol

Applicant:

Bataafse Petroleum Maatschappij N.V., The Hague

Representative: Dr. K. Schwarzhans, patent attorney, Munich 19, Romanplatz 10

Claimed priority: V. St. v. America November 30, 1956 (No. 625 222)

John Anderson, San Pedro, Calif., And Donald Stanley Meistrom,

Torrance, Calif. (V. St. Α.), Have been named as inventors

be polynuclear, and they can also be substituted with other substituents, e.g. B. with hydrocarbon residues, such as alkyl, alkenyl and cycloalkyl or cycloalkenyl radicals with halogen atoms, such as chlorine and bromine, or with ether and ester radicals. Examples of monohydric phenols are: phenol-3-vinylphenol, p-tert-butylphenol, p-tert-octylphenol, 3,5-dimethylphenol, 3,5-dibromo-4-allylphenol, 3-allylphenol, 3,5-dimethoxyphenol, 3-allyloxyphenol, 2-cyclohexenylphenol, m- (8-pentadecenyl) phenol, 2,4-diallylphenol, 2,4,6-triallylphenol, p-chlorophenol and p-isooctylphenol. The unsubstituted monohydric phenols and the alkyl- and alkenyl-substituted ones are particularly preferred monohydric phenols and chlorine-substituted monohydric phenols, which are less than Contain 18 and preferably fewer than 12 carbon atoms.

The monohydric phenols described above are added to the reaction mixture in amounts of 3 to 10 percent by weight, based on the weight of the polyhydric phenol, was added.

It is known per se, phenol condensation

209 519/478

to react products with polyhalohydrins and then the halogen atoms that have not reacted with monohydric phenols to react. In this way, very complex end products are created, which are highly viscous and do not have the desired properties of the glycidyl polyethers which can be prepared according to the invention.

The method according to the invention is technical Manufacture of glycidyl polyethers each

components can use different modes of operation, it is generally preferred to add the polyhydric phenol and the monohydric phenol to the aqueous solution containing the Contains alkali hydroxide, whereupon the mixture is heated and then the epihalohydrin is added will.

The ones used in the etherification reaction Temperatures generally vary between

suitable polyhydric phenol applicable. ₁₀ about 40 and about 15O ⁰ C and advantageously

Typical phenols are e.g. E.g .: resorcinol, hydroquinone, methylresorcinol, chlorohydroquinone, phloroglucinol, 1,5-dioxynaphthalene, 4,4'-dioxydiphenyl, bis (4-oxyphenyl) methane, l, l-bis- (4-oxyphenyl) -ethane, 1,1-bis- (4-oxyphenyl) -isobutane, 2,2-bis- (4-oxyphenyl) -propane, which for simplicity is called bisphenol, 2,2-bis- (4-oxyphenyl) -butane, 2,2-bis- (4-oxy-2-methyl) )-propane, 2,4'-Dioxydiphenyldimethylmethane, 2,2-bis- (2-chloro-4-oxyphenyl) -propane, 2,2-bis-

between 60 and 100 ° C. It is advisable to reflux the mixture slowly keep. The reaction is preferably carried out at atmospheric pressure.

The glycidyl polyether formed is then used to remove that formed in the reaction Salt expediently treated with a solvent that is available at the beginning of the manufacturing process or during the processing of the

(2-oxynaphthyl) pentane, 1,3-bis (4-oxyphenyloxy) - 20 reaction product can be added. Preferred 2-oxypropane and 3-oxyphenyl salicylate. but the solvent only becomes wise in the

Such polyvalent purification stages are particularly preferably added. For this purpose you can Phenols containing 6 to 30 carbon atoms and especially any solvents used with the suitably contain 6 to 20 carbon atoms. Saline solution are relatively difficult to mix

Although the application of epichlorohydrin for 25 and the glycidyl polyether are able to solve without the production of the new glycidyl polyethers before reacting with this, for example methyl iso-

butyl ketone, toluene, diisobutyl ketone, benzene, ethylbenzene or mixtures of such compounds.

The amount of solvent added should be sufficient to create a mobile organic liquid Phase to form with the reaction product, and in most cases solvents and polyethers applied in such an amount that solutions with a polyether content of about 20 to Epihalohydrin per mole of the phenol. Preferred 35 80% make up.

wisely, however, 2 to 25 moles of epihalohydrin are added.

used per mole of the dihydric phenol. When the solvent has been added, the To prepare the liquid glycidyl polyethers, the organic phase is washed with water to approx The best results obtained by applying to remove entrained salt. A single wash Ratio of 5 to 15 moles and especially 40 treatment may be sufficient. But it will be common expediently 5 to 10 moles of the epihalohydrin are washed twice or more frequently, per mole of the dihydric phenol. in order to achieve a satisfactory removal of the salt

Ensure the amount used in the procedure. It can also be beneficial substances Hydroxyds is mainly determined by the amount of in such as acetic acid or sodium di or monohydrogen reaction occurring epihalohydrin determined. So add 45 phosphate to the wash water to about

If desired, other epihalohydrins, such as epibromohydrin, can also be used will. Sodium hydroxide is generally preferred as the alkali.

According to the invention, more than 1 equivalent must be Epihalohydrin can be used. So if a dihydric phenol according to the present process is etherified, more than 1 mole is used

to neutralize unreacted hydroxide.

After adding the wash water, the mixture is allowed to stand for a short time until two separate Have formed layers. The aqueous phase is

This can be done by distillation or other suitable measures. If you distill, you have to care must be taken that no monomeric

one uses z. B. when etherifying a polyhydric phenol using an excess of more than 2 moles of epihalohydrin per phenolic hydroxyl equivalent, about 1 mole

Hydroxide per phenolic hydroxyl equivalent. For example, the preparation of the glycidyl poly solvent and any water carried along with it, ether of a dihydric phenol, is removed from the organic phase
an excess of epihalohydrin normally using about 1.8 to 2.5 moles,

preferably about 2.1 to 2.3 mol 'of the hydroxide 55 glycidyl ether is removed in the reaction mixture per mole of the dihydric phenol. as a result of the reaction of the monohydric phenol with

The alkali hydroxide can be present with the other reactants the epichlorohydrin,
tion components in any suitable manner to- The glycidyl poly-

be brought together. Although solid ethers of polyhydric phenols can be used for many hydroxides, it is one of the most common uses. As already preferred aqueous solution, z. B. one mentioned, its low viscosity makes it particularly containing about 5 to 30 percent by weight of the hydroxide. Good results are achieved with application
from about 10 to 20 percent by weight
aqueous hydroxide solutions. If desired, 65
a suspension of the hydroxide was also used
will.

Although to bring the reac-

suitable for use in the manufacture of adhesives, laminates and for the manufacture of Embedding and casting compounds.

The following examples explain the implementation the method according to the invention in more detail. Unless otherwise stated, the parts listed refer to the weight,

example 1

1 mole of bisphenol (2,2-bis (4-oxyphenyl) propane) was dissolved in 10 moles of epichlorohydrin and 1 to 2% water was added to the mixture. 5 weight percent phenol was then added to the mixture. The mixture was placed in a reaction vessel equipped with a heating and cooling device, stirrer, condenser and collecting vessel. The mixture was then heated to 80 ° C. and 2 moles of solid sodium hydroxide were added in small portions. During this addition, sufficient cooling was carried out to maintain the temperature at 95 to 97 ° C., with a slight distillation of epichlorohydrin and water occurring. After the last portion of the sodium hydroxide had been added at the end of the reaction, the excess epichlorohydrin was removed by vacuum distillation. After the distillation had ended, the residue was cooled to about 90 ° C. and about 300 parts of benzene were added. On cooling, the temperature of the mixture dropped to about 40 ^° C., with salt precipitating out of the solution. The salt was separated by filtration and the separated salt was carefully washed with about another 300 parts of benzene to remove polyether therefrom. The two benzene solutions were combined and distilled to separate the benzene. When the kettle temperature had reached 125 ° C., the distillation was continued under vacuum. The reaction product obtained was a liquid mixture which contained glycidyl polyether of bisphenol and had the following properties: epoxy value = 0.541, equivalents per 100 g; Color 6 (Gardner), chlorine content = 0.24 percent by weight; Viscosity = 70 poise.

A corresponding glycidyl polyether of bisphenol, which in the same way as described above, but was made without adding the monohydric phenol, had a viscosity of 150 poise at 25 ° (and an epoxy value of 50 equivalents per 100 g).

The difference in properties between those according to the present invention as described above and a product obtained by adding phenyl glycidyl ether as a diluent to the common glycidyl polyether of bisphenol found in US Pat in the way mentioned in the last paragraph, can be seen from the following:

According to the method not claimed here, an adhesive was produced by mixing 100 parts of the mass produced according to the invention according to the first paragraph of Example 1 with asbestos filler and 8 parts of diethylaminopropylamine prepared. This mixture was between two aluminum foils brought and cured the entire product at 100 ° C. The composite body obtained had a Tear strength of 272.3 kg / cm2 at 82 ° C. A similar composite body made from a mass the just the simple preformed glycidyl ether of bisphenol, as described above, as well 5% added phenyl glycidyl ether, had a tear strength at 82 ° C of only 174.3 kg / cm2. A composite made from the simple preformed glycidyl ether of bisphenol (as described above) and without the addition of phenyl glycidyl ether, had a tear strength of 243.1 kg / cm2 at 82 ° C.

100 parts of the resin prepared according to the invention according to the first paragraph of the above example were by a method not claimed here with 10 parts of a 2-ethylcaproic acid salt of 2,4,6-Tris- (dimethylaminomethyl) -phenol heated at 65 ° C for 2 hours. The body received had a Barcol hardness of 34. A similar body made from the common glycidyl ether of bisphenol, obtained without the addition of ίο monohydric phenol, also had a Barcol hardness of 34. Both bodies showed good flexibility and were very resistant to impact in the cold.

Example 2

The reaction according to the first paragraph of Example 1 was repeated with the difference that the amount of phenol added was 1% instead of 5%. The product obtained was a liquid resin with a viscosity of about 120 poise at 25 ° C, a Gardner color of 4 to 5, with 0.25% chlorine content and an epoxy weight of 189.

A hardened body produced by a method not claimed here, which by heating of 100 parts of the resin with 10 parts of the 2-ethylcaproic acid salt of 2,4,6-tris (dimethylaminomethyl) phenol as prepared in Example 1, had a Barcol hardness of 34.

The resin prepared as described above was converted into a process not claimed here an adhesive produced and processed with aluminum as in Example 1. This also resulted excellent strength at higher temperatures.

Example 3

The procedure according to the first paragraph of Example 1 was repeated with the exception that 13% phenol was added instead of 5%. The resulting resin was a liquid mass having a viscosity of about 27 poise at 25 ° C, a Gardner color of 3 to 4, a chlorine content of 0.25% and an epoxy equivalent weight of 186.
A hardened body made from this process not claimed here by heating 100 parts of the resin with 10 parts of the 2-ethylcaproic acid salt of 2,4,6-tris (dimethylaminomethyl) phenol as in Example 1 had a Barcol hardness from 35.

An adhesive produced from this resin by a method not claimed here, which becomes a Composite body made of aluminum was processed according to Example 1, also had an excellent Strength at higher temperatures.

Example 4

The procedure according to the first paragraph of Example 1 was repeated with the difference that 8.7% phenol was added instead of 5%. The product obtained was a liquid mass with a Viscosity of about 46 poise at 25 ° C, a Gardner color of 4, a chlorine content of 0.26% and an epoxy equivalent weight of 187.

A method not claimed here by heating 100 parts of this resin with 10 parts of a 2-ethylcaproic acid salt of 2,4,6 tris (dimethylaminomethyl) phenol as in the example 1 hardened body produced had one

Barcol hardness of 35. One from the aforesaid resin using a method not claimed here produced adhesive mixture, which was used for joining aluminum according to example 1, also showed excellent strength at 5 higher temperatures.

Example 5

Compounds with similar properties can be obtained by adding the monohydric phenol in i ° - the examples Γ to 4 replaced by equal amounts of one of the following compounds: p-tert-butylphenol; 3,5-dimethylphenol or p-octylphenol.

Example 6 "

The production method according to the first paragraph of Example 1 was repeated, but 3.1% Phenol were added. The product obtained was a liquid mass with a viscosity of 84 poise at 25 ° C.

A method not claimed here by heating 100 parts of the resin with a equivalent amount of hexahydrophthalic anhydride obtained hardened body was very hard and had excellent resistance to solvents.

Claims (7)

PATENT CLAIMS: 1. A method for producing a Glycidylpolyäthers from a polyhydric phenol and epichlorohydrin in an alkaline medium, characterized in that a polyhydric phenol having more will be implemented as the equivalent amount of epihalohydrins and with an alkali metal hydroxide in the presence of 0.1 to 13 weight percent of a monohydric phenol . 2. The method according to claim 1, characterized in that an unsubstituted or a alkylated monohydric phenol is used. 3. The method according to claim 1 or 2, characterized in that the monohydric phenol in in an amount of 3 to 10% calculated on the weight of the polyhydric phenol will. 4. The method according to claim 1 to 3, characterized in that a polyhydric phenol with 6 to 30 carbon atoms is used. 5. The method according to claim 1 to 4, characterized in that per mole of the divalent Phenol 2 to 25 moles of epihalohydrin can be used. 6. The method according to claim 1 to 5, characterized in that the alkali hydroxide in one Amount of about 1 mol per phenolic hydroxyl equivalent of the polyhydric phenol is used. 7. The method according to claim 1 to 6, characterized in that the reaction is carried out at a temperature between 40 and 150 ^0C . Considered publications:
German patent specification No. 576 177. © 209 519/478 3.